GB2066802A - Refractory for casting - Google Patents
Refractory for casting Download PDFInfo
- Publication number
- GB2066802A GB2066802A GB8041227A GB8041227A GB2066802A GB 2066802 A GB2066802 A GB 2066802A GB 8041227 A GB8041227 A GB 8041227A GB 8041227 A GB8041227 A GB 8041227A GB 2066802 A GB2066802 A GB 2066802A
- Authority
- GB
- United Kingdom
- Prior art keywords
- weight
- refractory
- nozzle
- chemical composition
- total weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D41/00—Casting melt-holding vessels, e.g. ladles, tundishes, cups or the like
- B22D41/50—Pouring-nozzles
- B22D41/52—Manufacturing or repairing thereof
- B22D41/54—Manufacturing or repairing thereof characterised by the materials used therefor
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
- C04B35/101—Refractories from grain sized mixtures
- C04B35/103—Refractories from grain sized mixtures containing non-oxide refractory materials, e.g. carbon
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
- C04B35/101—Refractories from grain sized mixtures
- C04B35/106—Refractories from grain sized mixtures containing zirconium oxide or zircon (ZrSiO4)
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/482—Refractories from grain sized mixtures
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/632—Organic additives
- C04B35/634—Polymers
- C04B35/63496—Bituminous materials, e.g. tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/66—Monolithic refractories or refractory mortars, including those whether or not containing clay
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0087—Uses not provided for elsewhere in C04B2111/00 for metallurgical applications
- C04B2111/00887—Ferrous metallurgy
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
- C04B2235/3244—Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3427—Silicates other than clay, e.g. water glass
- C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3817—Carbides
- C04B2235/3826—Silicon carbides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/38—Non-oxide ceramic constituents or additives
- C04B2235/3852—Nitrides, e.g. oxynitrides, carbonitrides, oxycarbonitrides, lithium nitride, magnesium nitride
- C04B2235/3873—Silicon nitrides, e.g. silicon carbonitride, silicon oxynitride
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
- C04B2235/9676—Resistance against chemicals, e.g. against molten glass or molten salts against molten metals such as steel or aluminium
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Composite Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Casting Support Devices, Ladles, And Melt Control Thereby (AREA)
Abstract
A refractory for steel casting comprising, based on the total weight of the refractory in each case, 5-80% by weight of ZRM, 10-40% by weight of carbon powder, 0-20% by weight of one or more of SiC, Si3N4, metallic silicon and ferrosilicon, 0-30% by weight of fused silica and 0-60% by weight of alumina powder containing at least 70% by weight of Al2O3 based on the total weight of the alumina powder. The ZRM includes the main mineral phase consisting of mullite, baddeleyite and corundum and having the chemical composition consisting of 25-85% by weight of Al2O3, 10-70% by weight of ZrO2 and 5-25% by weight of SiO2. A process for producing the refractory for steel casting, and a refractory nozzle are also described.
Description
SPECIFICATION
Refractory for casting and process for producing same
This invention relates to a highly-durable carbon powder-containing refractory for steel casting and more particularly, to a highly durable carbon-containing refractory nozzle system of a casting machine and a process for producing such a refractory nozzle system.
Of late, with the aim to increase the yield rate and reduce the cost in the production of steel castings, the so-called continuous charge casting system has been increasingly employed in place of the so-called batch charge system and, particularly in recent years, the steel casting operation has been in most cases consecutively performed from several charges up to several tens of charges.
In a steel casting machine, the refactory nozzle is employed between the ladle tundish and between the tundish and mould, respectively, and serves to prevent oxidation of molten steel and regulate the flow direction of the molten steel. Thus, the refractory nozzle is a quite important refractory component in the steel casting machine.
However, when the refractory nozzle is employed in the continuous casting operation referred to hereinabove, since the nozzle tends to be submerged in the molten steel pool for a fairly long time period, the portion of the nozzle which is designed to come to contact with a highly erosive powder layer such as silica or alumina which is spread over the top of the molten steel pool is attacked by the erosive powder.
In order to protect the particular portion of the refractory nozzle from the erosive material, various attempts have been made up to date. The conventional attempts are (1) the formation of the nozzle with Awl203 and graphite, (2) the mounting of a protective ring on the powder-contacting portion of the nozzle brick and (3) the simultaneous formation of the powder-contacting portion and the rest of the refractory nozzle by the use of a high erosion resistance material (for example, zirconia or the like) and steel, respectively, to thereby reinforce the refractory nozzle powder contacting portion. However, none of these conventional attempts have been found perfectly satisfactorv.Although the attempt (3) has been extensively studied and widely practiced because the attempt can use the expensive material such as zirconia with a high efficiency, since the nozzle is formed of a combination of different materials, this nozzle encounters difficulty in the formation of the same. In addition, the powder contacting portion of the nozzle formed of the different material combination can not be always maintained in contact with the powder layer over the molten steel pool because the refractory nozzle moves upwardly and downwardly in the casting operation to thereby render some portion of the refractory nozzle other than the powder contacting portion thereof to be exposed to the erosive powder layer which may result in giving damage to the area adjacent to the powder contacting portion of the nozzle and, thus, the attempt has been found not perfectly satisfactory.
When a long nozzle the tip of which is adapted to be always submerged in the molten steel pool during the casting operation is employed, the submerged tip of the nozzle is attached by the heat of the molten steel flowing down through the refractory nozzle and wears away prematurely to thereby reduce the designed service life of the nozzle. Furthermore, when a submerged nozzle is used, alumina deposit from the molten steel tends to adhere to the orifices in the nozzle to clog them up, which may also reduce the service life of the nozzle.
In order to prevent the nozzle orifices from being clogged up by the alumina deposit from the molten steel, it has been proposed to blow gas such as argon gas into the orifices. However, in the conventional refractory nozzle formed of a combination of Al203 and graphite, the alumina deposit cannot be perfectly removed from the orifices and such gas blowing has been found not fully effective.
Also the gas blowing tends to disturb the molten steel pool to thereby accelerate the wearing away of the refractory nozzle. The wearing away progresses from the walls of the refractory nozzle orifices into the body of the nozzle.
Thus, there has been a demand for a nozzle for use in the continuous steel casting operation which can effectively solve the problem of orifice clogging-up by alumina deposit without the blowing of gas or by full realization of the effects of gas blowing of gas blowing and that of wearing-off of the nozzle.
A patent has been granted to the formation of a highly durable nozzle for the continuous steel casting operation with a combination of Awl203 and graphite with zircon or zirconia added thereto.
However, since zircon or zirconia is employed in its original form, such additive cannot be perfectly and uniformly distributed within the Al203 and graphite combination. In addition, since zircon and zirconia have a higher fire resistance than those of the other components of the refractory nozzle, such additive materials take a rather long time period until they form a highly viscous glass film through their reaction with the other refractory nozzle components and the other components tend to be adversely affected by the heat of molten steel before the glass film is formed.
In order to prevent the refractory nozzle orifice clogging-up problem, although it has been proposed to add silica in an increased amount to the Awl203 and graphite combination, the addition of such increased amount of silica is still not able to appreciably reduce the possibility of refractory nozzle orifice clogging-off. Also, it is difficult to increase the amount of additive in proportion to the amount of alumina deposit to prevent wearing-off and orifice clogging-up whereby the additive cannot be added in an amount to cope with variation in the type of steel material to be cast.
Therefore, the purpose of the present invention is to provide a novel and improved highly durable refractory for nozzles for use in continuous steel casting which can effectively eliminate the disadvantages inherent in the conventional refractory nozzle and be continuously employed for a long time period and a process for producing the refractory.
The inventors have previously developed a highly durable refractory nozzle for use in the continuous steel casting based on steel casting based on a refractory being formed of an electrically fused or burnt refractory material clinker comprising a refractory component including the principal mineral phase consisting of mullite, baddeleyite and corundum and having the chemical composition consisting of Al203, ZrO2 and SiO2 within a certain blending ration (the refractory material clinker wiil be referred to as "ZRM" hereinafter); thus the refractory nozzle is the subject of Japanese Patent
Application No 87459/1979.As disclosed in this Japanese patent application, the highly durable refractory nozzle for use in the continuous steel casting is prepared by admixing, based on the total weight of the refractory in each case, a refractory component including the principal mineral phase consisting of mullite, baddeleyite and corundum and having the chemical composition consisting of 30-60% by weight of Al2O, 20-60% by weight of ZrO2 and 525% by weight of SiO2 base on the weight of the chemical composition, respectively, 20-40% by weight of graphite powder, 0-10% by weight of SiC, 0-25% by weight of fused silica and 0-45% by weight of alumina powder containing at least 70% by weight of Al203 based on the weight of the alumina powder at a cold temperature or under heating by the use of resin or pitch binder, moulding the mixture and burning the moulded product in non-oxidation atmosphere.
However, through subsequent researches, the inventors have found that the ZRM nozzle positively forms higly viscous glass films thereon with the heat from molten steel to thereby improve the heat resistance of the inner and outer surfaces of the nozzle, that the presence of the thus formed glass films on the inner and outer surfaces of the refractory nozzle improve wear resistance and anti-orifice clogging-off of the refractory nozzle and that the nozzle has imparted thereto a high durability even when the blending ratio of the components in the refractory component and the blending amount of the refractory component in the refractory are varied within a certain range and particularly, even when the refractory component is employed in the mixture in amounts ranging from 530% by weight based on the total weight of the mixture, the highly durable nozzle for casting to which the present invention is directed can be employed.
According to the present invention, a highly durable refractory nozzle for use in the continuous steel casting can be provided by admixing, based on the total weight of the mixture in each case, 5-80% by weight of refractory component including the principal mineral phase consisting of mullite, baddeleyite and corundum and having the chemical composition consisting of 2585% by weight of Al203, 10-70% by weight of ZrO2 and 5-25% by weight of SiO2, respectively, based on the total weight of the chemical composition, 10-40% by weight of graphite powder, 0-20% by weight of one or more members selected from SiC, Si3N4, metallic silicon and ferrosilicon, 0-30% by weight of fused silica and 0-60% by weight of alumina containing at least 70% by weight of Al203 based on the total weight of the alumina powder at cold temperature of under heating by the use of resin or pitch binder, moulding the mixture and burning the moulded mixture in non-oxidation atmosphere.
As to the refractory component including the principal mineral phase consisting of mullite, baddeleyite and corundum and having the chemical composition consisting of 2585% by weight of Al203, 10-70% by weight of ZrO2 and 5-25% by weight of SiO2 based on the total weight of the chemical composition, clinker prepared by fusing zircon and alumina as principal materials or clinker prepared by fusing zircon and alumina with the addition of baddeleyite thereto can be employed. The present invention is not limited to the use of ZRMs prepared by fusing zircon and alumina with or without the addition of baddeleyite thereto, but clinkers prepared by sintering zircon and alumina with or without the addition of baddeleyite thereto and grinding the sinter to adjust the grain size thereof can be also employed.
Zirconia has an excellent erosion resistance and, as mentioned hereinabove, although zirconia is suitably employed to reinforce the powder contacting portion of the- refractory nozzle, the material is prohibitively expensive. In addition, since zirconia has a relatively high specific gravity and as a result, the erosion resistance material adds weight to the resulting refractory nozzle to thereby make it inconvenient to handle the refractory nozzle. On the other hand, stabilized zirconia has a higher coefficient of thermal expansion than those of oxides such as corundum and zircon which are employed as the principal components of a carbon-containing submerged nozzle. Unstabilized zirconia tends to expand excessively to the extent that the material cracks.
With the aim to provide a nozzle for use in steel casting which has spalling, wear and orifice clogging-up resistance properties and which can form a glass film easily while retaining excellent erosion resistance against the erosive powder layer, the inventors have conducted extensive researches on various materials and have found that in ZRM zirconia crystals deposit within and about mullite and corundum crystals to protect the mullite and corundum crystals and the zirconia crystals exhibit excellent erosion resistance effect. Also since ZRM has a relatively lower resistance as compared with alumina, zirconia and zircon, ZRM can easily form a glass film in which zirconia is dispersed and has a high viscosity.Furthermore, ZRM has a relatively low coefficient of thermal expansion such as 7 x 10-6 and is characterised by its low coefficient of thermal expansion such as 2-4 x 10-6 within the high temperature range of 1000-1 6000 C. The inventors have come to the conclusion that these properties of ZRM suitable as the principal refractory component for submerged nozzles for use in continuous steel casting which is required to have high erosion, wear, orifice clogging-up and spalling resistance properties.
When ZRM contains ZrO2 in amounts less than 10% by weight based on the total weight of ZRM,
the amount of zirconia which deposits within and about mullite and corundum crystals is insufficiently small and ZrO2 in such small amounts fails to improve the erosion resistance of the nozzle. On the other
hand, when the amount of ZrO2 exceeds 70% by weight, since the ZrO2 is present in the form of
monoclinic crystals, any abnormal expansion occurs in ZrO2 to thereby undesirably reduce the spalling resistance of the nozzle. Thus, the amount of ZrO2 to be contained in ZRM should be within the range of 1070% by weight based on the total weight of ZRM.In ZRM the amounts of Al203 and SiO2 should be
within the ranges of 2589% by weight and 5-25% by weight, respectively, based on the total weight of ZRM. 4
ZRM having the above-mentioned chemical composition occupies 580% by weight based on the total weight of the mixture for the refractory nozzle. When ZRM is employed in amounts less than
5% bv weight in the mixture, the above-mentioned properties of ZRM cannot exhibit their full effects, on the other hand, when the amount of ZRM exceeds 80% by weight, the spalling resistance property of the resulting submerged nozzle is insufficient.
The amount of graphite in the mixture should be within the range of 1040% by weight based on the total weight of the mixture. When graphite is employed in amounts less than 10% by weight, the resulting nozzle has insufficient erosion and spalling resistances. On the other hand, when the amount of graphite exceeds 40% by weight, graphite melts into the molten steel pool and presents an impurity in the molten steel. In place of graphite, amorphous graphite, acheson graphite, kish graphite, thermally decomposed graphite, petroleum pitch coke, coal coke, anthracite, charcoal, carbon black, thermally decomposed carbon of carbonhydride, thermally decomposed carbon of carbon hydrate, thermally decomposed carbon of synthetic resin or glassy carbon can be equally employed within the scope of the invention.
The amount of the one or more members selected from the group consisting of SiC, Si3N4, Metallic silicon and ferrosilicon should be within the range of 0-20% by weight and the one or members of the group form a SiO2 glass film when they oxidize. The glass film contributes to the prevention of oxidation. When the amount of the one or more members of the group exceeds 20% by weight, the material or materials melt into the molten steel pool and present impurity or impurities in the molten metal. The amount of fused silica should be within the range of 0-30% by weight based on the total weight of the mixture and the fused silica in amounts within the range serve to impart spalling and orifice clogging-up resistance properties to the resulting nozzle.When silica is employed in amounts in excess of 30% by weight, the nozzle tends to be damaged by the molten metal.
The amount of alumina containing up to 70% by weight of Awl203 based on the total weight of the alumina should be within the range of 0-60% by weight based on the total weight of the refractory mixture. However, since Al2O3 is also contained in ZRM, alumina is added to the refractory mixture as the case may be.
According to the present invention, the abovementioned components of the refractory mixture are mixed together by the use of resin or pitch binder at cold temperature or under heating, the resultirg refractory mixture is moulded and the moulded product is burnt in a non-oxidation environment.
Examples of the present invention will be given hereinbelow by way of illustration together
with controls for comparison purpose, but not for limiting the present invention thereto.
Table 1 shows properties of various ZRMs employed as the principal components in the production of refractory mixtures for nozzles for use in continuous steel casting, and Tables 2 and 3 show various blending ratios of ZRMs and other components together with properties of refractory mixtures obtained. In each case, the mixing was carried out by the use of an airich mixer, the moulding was carried out by the use of a rubber press under the pressure of 1200 kg/cm2 and the burning was carried out by the conventional practice with the moulded product embedded in coke. It has been found that nozzles formed of the refractory mixtures containing ZRMs exhibited excellent orifice clogging-up, wear and spalling resistance properties and also erosion resistance property against erosive powder layer.No cracks occurred in the powder contacting portions of the nozzles and the obtained nozzles are superior to the conventional comparative nozzles.
TABLE 1
Properties of ZRM
Chemical Composition Coefficient of Thermal By weight (%) Physical Property Expansion (%) Bulk Specific Apparent Porosity No. ZrO2 Al2O3 SiO2 Gravity (%) At 1000 C Abnormality ZRM 1 10.0 67.0 18.0 3.05 4.0 0.65 none ZRM 2 35.0 63.0 16.0 3.15 4.1 0.65 none ZRM 3 35.0 48.0 16.0 3.65 2.5 0.70 slight ZRM 4 45.0 40.0 14.0 3.80 2.9 0.80 slight ZRM 5 55.0 33.0 10.0 3.95 2.7 0.70 slight ZRM 6 70.0 20.0 10.0 4.20 3.1 0.70 medium ZRM 7 80.0 13.0 5.0 4.35 3.8 0.75 great TABLE 2-A (By weight %)
Control 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Crystalline flaky graphite 30 30 30 30 30 30 30 ZRM 5 15 30 30 30 60 (ZRM 3) (ZRM 4) (ZRM 4 (ZRM 4) (ZRM 4) (ZRM 4) Electrically fused alumina 60 50 40 30 15 10 Fused silica 5 5 15 20 Silicon carbide 5 5 5 5 5 5 5 Metallic silicon 5 5 5 5 5 5 5 Phenol resin binder +10 +10 +10 +10 +10 +10 +9.5 Bulk specific gravity 2.48 2.43 2.45 2.65 2.51 2.40 2.59 Apparent porosity (%) 18.0 18.5 18.8 18.7 18.3 19.3 20.1 Crushing strenght (kg/cm) 350 280 290 315 300 280 310 Spalling resistance (1500* cracks occurred none none none none none no crack C x 15 minute water cooling, at 3rd repeated 4 times) water cooling Corrosion resistance index 100 93 90 77 95 100 55 Number of charges with 3 5 5 5 5 5 6 tundish for 200 # ladle charges charges charges charges charges charges charges Number of charges with 1 1 1 - - - tundish for 50 # ladle charge charge charge TABLE 2-B (By weight %)
Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Crystalline flaky graphite 30 30 20 30 25 20 ZRM 60 60 60 60 70 80 (ZRM 5) (ZRM 3) (ZRM 4) (ZRM 6) (ZRM 3) (ZRM 3) Electrically fused alumina Fused silica 10 Silicon carbide 5 5 5 5 Metallic silicon 5 5 5 5 5 Phenol resin binder +9.5 +9.5 +9 +9.5 +9 +9 Bulk specific gravity 2.69 2.57 2.72 2.71 2.74 2.76 Apparent porosity (%) 19.7 18.8 18.4 19.1 19.6 20.0 Crushing strenght (kg/cm) 320 280 305 275 280 280 Spalling resistance (1500* no crack no crack no crack fine cracks occurred fine cracks occurred no crack x 15 minute water cooling, at 4th at 4th repeated 4 times) water cooling water cooling Corrosion resistance index 45 70 55 45 40 35 Number of charges with 6 6 - - - tundish for 200 # ladle charges charges Number of charges with - - 2 2 2 2 tundish for 50 # ladle charges charges charges charges TABLE 2-C (By weight %)
Control 2 Control 3 Control 4 Control 5 Control 6 Control 7 Crystalline flaky graphite 30 20 30 30 30 30 ZRM 60 70 40 30 60 20 (zirconia) (zirconia) (zirconia) (zircon) (zircon) (zirconia) (zircon) 20 Electrically fused alumina 20 30 20 Fused silica Silicon carbide 5 5 5 5 5 5 Metallic silicon 5 5 5 5 5 5 Phenol resin binder +8.5 +8 +9.5 +10 +10 +9.5 Bulk specific gravity 2.70 3.15 2.64 2.53 2.62 2.66 Apparent porosity (%) 20.3 19.7 20.1 18.3 18.5 17.9 Crushing strenght (kg/cm) 250 330 260 280 330 290 Spalling resistance (1500 C cracks occurred cracks occurred cracks occurred no crack no crack crack occurred x 15 minute water cooling, at 2nd at 1st at 2nd at 3rd repeated 4 times) water cooling water cooling water cooling water cooling Corrosion resistance index 40 30 70 105 90 85 Number of charges with 4 charges, - 4 3 - 3 tundish for 100 # ladle cracks occurred charges charges charges Number of charges with 1 - - - 1 tundish for 50 # ladle charge charge TABLE 3 (By weight %)
Example 13 Example 14 Example 15 Example 16 Control 8 Control 9 Control 10 long nozzle submerged nozzle submerged nozzle long nozzle submerged nozzle submerged nozzle Crystalline flaky graphite 30 30 30 30 30 30 30 ZRM 5 10 25 20 - - (ZRM 3) (ZRM 3) (ZRM 3) (ZRM 3) Electrically fused alumina 40 35 22 35 45 47 55 Fused silica 20 20 15 5 20 15 5 Silicon carbide 5 5 5 5 5 5 5 Metallic silicon - - 3 5 - 3 5 Phenol resin binder +10 +10 +10 +10 +10 +10 +10 Bulk specific gravity 2.25 2.25 2.30 2.40 2.25 2.30 2.40 Apparent porosity (%) 14.5 14.5 16.5 17.0 14.5 17.0 17.5 Crushing strenght (kg/cm) 270 290 240 270 255 245 280 Spalling resistance (water no crack no cracks no crack no crack no crack no crack no crack cooling for 15 min. at 1500 C repeated 4 times) Number of charges with 11 13 - - 6 - *1 *2 *1 *2 200 # ladle charges charges charges Number of charges with - - 4 charges 6 charges - 2 charges 5 charges tundish for 200 # ladle no trouble orifice substantial clogging-off damage by heat Note: *1 = higt aluminium steel, gas bubbling and laminated layers of zirconia and graphite.
*2 = medium aluminium steel, gas bubbling and laminated layers of zirconia and graphite.
Claims (13)
1. A highly durable refractory for casting comprising, based on the total weight of said refractory in each case, 5-80% by weight of refractory component including the principal mineral phase consisting of mullite, baddeleyite and corundum and having the chemical composition consisting of 2585% by weight of Al2O3, 10-70% by weight of ZrO2 and 5-25% by weight of SiO2, respectively, based on the total weight of said chemical composition, and 1 0-40% by weight of carbon powder.
2. The highly durable refractory for casting as set forth in Claim 1, further comprising, based on the total weight of said refractory in each case, up to 20% by weight of one or more members selected from the group consisting of SiC, Si3N4, metallic silicon and ferrosilicon, up to 30% by weight of fused silica and up to 60% by weight of alumina powder containing at least 70% by weight of Al203 based on the total weight of said alumina powder.
3. A process for producing a highly durable refractory for casting comprising the steps of admixing.
based on the total weight of said refractory in each case, 5-80% by weight of refractory component including the principal mineral phase consisting of mullite, baddeleyite and corundum and having the chemical composition consisting of 2585% by weight of Al203, 10-70% by weight of ZrO2 and 5-25% by weight of SiO2, respectively, based on the total weight of said chemical composition and 1040% by weight of carbon powder, by the use of a binder, moulding said mixture and burning the resulting moulded product in non-oxidation environment.
4. A process for producing a highly durable refractory for casting comprising the steps of admixing, based on the total weight of said refractory in each case, 5-80% by weight of refractory component including the principal mineral phase consisting of mullite, baddeleylite and corundum and having the chemical composition consisting of 2585% by weight of Al2O3, 10-70% by weight of ZrO2 and 525% by weight of SiO2, respectively, based on the total weight of said chemical composition, 10-40% by weight of carbon powder, up to 20% by weight of one or more members selected from the group consisting of SiC, Si3N4, metallic silicon and ferrosilicon, up to 30% by weight of fused silica and up to 60% by weight of alumina powder containing at least 70% by weight of Al203 based on the total weight of said alumina powder by the use of a binder, moulding said mixture and burning the resulting moulded product in non-oxidation environment.
5. The process as set forth in Claim 3 or Claim 4 in which said binder is resin.
6. The process as set forth in Claim 3 or Claim 4, in which said binder is pitch.
7. The process as set forth in any one of claims 3 to 6, in which said admixing step is performed at cold temperature.
8. The process as set forth in any one of Claims 3 to 6, in which said admixing step is performed under heating.
9. A highly durable refractory nozzle for casting comprising, based on the total weight of said refractory in each case, 5-80% by weight of refractory component including the principal mineral phase consisting of mullite, baddeleyite and corundum and having the chemical composition consisting of 2585% by weight of Al203, 10-70% by weight of ZrO2 and 5-25% by weight of SiO2, respectively, based on the total weight of said chemical composition, and 10-40% by weight of carbon powder.
1 0. A process for producing a highly durable refractory nozzle for casting comprising the steps of admixing, based on the total weight of said refractory in each case, 5-80% by weight of refractory component including the principal mineral phase consisting of mullite, baddeleyite and corundum and having the chemical composition consisting of 25-85% by weight of Al203, 10-70% by weight of
ZrO2 and 5-25% by weight of SiO2, respectively, based on the total weight of said chemical composition, 10-40% by weight of carbon powder, up to 20% by weight of one more members selected from the group consisting of SiC, Si3N4, metallic silicon and ferrosilicon, up to 30% by weight of fused silica and up to 60% by weight of alumina powder containing at least 70% by weight of Al2O3 based on the total weight of said alumina powder, by the use of a binder, moulding said mixture and burning the resulting moulded product in non-oxidation environment.
11.A refractory nozzle for use in steel casting,substantially as hereinbefore described with reference to any of the Examples of the invention.
12. A process for producing a refractory nozzle for use in steel casting, substantially as hereinbefore described.
13.The features herein described,or their equivalents,in any novel selection.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP54170307A JPS5919067B2 (en) | 1979-12-28 | 1979-12-28 | High durability casting nozzle |
Publications (2)
Publication Number | Publication Date |
---|---|
GB2066802A true GB2066802A (en) | 1981-07-15 |
GB2066802B GB2066802B (en) | 1983-05-11 |
Family
ID=15902537
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB8041227A Expired GB2066802B (en) | 1979-12-28 | 1980-12-23 | Refractory for casting |
Country Status (4)
Country | Link |
---|---|
US (1) | US4326040A (en) |
JP (1) | JPS5919067B2 (en) |
DE (1) | DE3048678A1 (en) |
GB (1) | GB2066802B (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2119359A (en) * | 1982-04-30 | 1983-11-16 | Tioxide Group Plc | Refractory lined vessel and method of use |
EP0117935A1 (en) * | 1983-06-03 | 1984-09-12 | Kato, Seiichi | A high emissivity refractory coating, process for manufacturing same, and coating composition therefor |
DE3413128A1 (en) * | 1984-04-06 | 1985-10-24 | Hitachi, Ltd., Tokio/Tokyo | Refractory material having a high aluminium oxide content for use in a nonferrous-metal smelting furnace |
DE3707884A1 (en) * | 1986-03-13 | 1987-09-17 | Toshiba Ceramics Co | CASTING NOZZLE AND METHOD FOR THEIR PRODUCTION |
EP0323010A2 (en) * | 1987-12-28 | 1989-07-05 | Shinagawa Refractories Co., Ltd. | Carbon containing refractory |
US4917276A (en) * | 1987-07-15 | 1990-04-17 | Kurosaki Refractories Co., Ltd. | Sliding gate nozzle for special steel |
CN114455941A (en) * | 2022-01-19 | 2022-05-10 | 北京科技大学 | Silicon-corundum-high titanium mullite composite refractory material for blast furnace and preparation method thereof |
Families Citing this family (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3237188C2 (en) * | 1982-10-07 | 1986-03-27 | Toshiba Ceramics Co., Ltd., Tokio/Tokyo | Method of making a pouring nozzle |
US4585485A (en) * | 1983-01-24 | 1986-04-29 | Hiroshi Shikano | Refractory sliding nozzle plate |
JPS6096567A (en) * | 1983-10-29 | 1985-05-30 | ハリマセラミック株式会社 | Manufacture of sliding nozzle plate |
DE3445559C1 (en) * | 1984-12-14 | 1986-08-14 | Martin & Pagenstecher GmbH, 5000 Köln | Refractory, thixotropic vibration mass as well as method and device for the vibration delivery of metallurgical vessels with this mass |
US4639427A (en) * | 1985-06-28 | 1987-01-27 | Norton Company | Stress-corrosion resistant proppant for oil and gas wells |
JPS62241869A (en) * | 1986-04-12 | 1987-10-22 | 川崎炉材株式会社 | Manufacture of zirconia base refractories |
JPS63117467U (en) * | 1987-01-23 | 1988-07-29 | ||
FR2647105B1 (en) * | 1989-05-22 | 1991-07-12 | Vesuvius France Sa | WATERPROOF COATING FOR REFRACTORY MATERIAL, COATED PART THEREOF, AND COATING METHOD |
US5214010A (en) * | 1990-09-24 | 1993-05-25 | Indresco, Inc. | Alumina-carbon compositions and slidegate plates made therefrom |
AU694643B2 (en) * | 1995-05-09 | 1998-07-23 | Toshiba Ceramics Co., Ltd. | Refractory for casting and method of manufacturing the same |
US6158248A (en) * | 1998-02-26 | 2000-12-12 | Asahi Glass Company Ltd. | Fused-cast-alumina-zirconia-silica refractory, methods of making it and glass melting furnace employing it |
CN101925558B (en) * | 2008-01-30 | 2013-06-19 | 黑崎播磨株式会社 | Raw material for zirconia/mullite refractory and plate brick |
CN102584301B (en) * | 2012-03-09 | 2013-04-17 | 西安建筑科技大学 | Method for preparing zirconium oxide sizing nozzle |
KR101303812B1 (en) | 2012-03-30 | 2013-09-04 | 한국과학기술연구원 | Alumina coated spinel-silicon carbide refractory compositions with high corrosion resistivity to coal slag and manufacturing method thereof |
PL2792656T3 (en) | 2013-04-19 | 2017-05-31 | Calderys France | Method for producing a silicon carbide whisker-reinforced refractory ceramic composition |
WO2016176758A1 (en) * | 2015-05-07 | 2016-11-10 | Les Produits Industriels De Haute Temperature Pyrotek Inc. | Article made from refractory material for contact with a liquid metal or alloy, a method for manufacture, use and method of use of same |
DE102015119053A1 (en) * | 2015-11-05 | 2017-05-11 | Center For Abrasives And Refractories Research & Development C.A.R.R.D. Gmbh | Sintered refractory zircon mullite composite, process for its preparation and its use |
CN110483077A (en) * | 2019-08-23 | 2019-11-22 | 河南恒耐尔耐火材料有限公司 | A kind of corundum wear-resistant castable and preparation method thereof |
CN111410521A (en) * | 2020-04-26 | 2020-07-14 | 河南兴亚能源有限公司 | Homogenized alumina non-oxide composite material castable and preparation method thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL7109435A (en) * | 1970-07-13 | 1972-01-17 | ||
US3752372A (en) * | 1971-04-20 | 1973-08-14 | Southwire Co | Clay-graphite spout |
JPS5338283B2 (en) * | 1972-05-19 | 1978-10-14 | ||
JPS583992B2 (en) * | 1974-11-30 | 1983-01-24 | ニホンルツボ カブシキガイシヤ | Lenzokuchiyuzoyoushinseki nozzle |
US4066467A (en) * | 1977-02-18 | 1978-01-03 | Chicago Fire Brick Company | Aluminous refractory composition containing carbon |
-
1979
- 1979-12-28 JP JP54170307A patent/JPS5919067B2/en not_active Expired
-
1980
- 1980-12-23 GB GB8041227A patent/GB2066802B/en not_active Expired
- 1980-12-23 DE DE19803048678 patent/DE3048678A1/en active Granted
- 1980-12-24 US US06/220,468 patent/US4326040A/en not_active Expired - Lifetime
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2119359A (en) * | 1982-04-30 | 1983-11-16 | Tioxide Group Plc | Refractory lined vessel and method of use |
EP0117935A1 (en) * | 1983-06-03 | 1984-09-12 | Kato, Seiichi | A high emissivity refractory coating, process for manufacturing same, and coating composition therefor |
DE3413128A1 (en) * | 1984-04-06 | 1985-10-24 | Hitachi, Ltd., Tokio/Tokyo | Refractory material having a high aluminium oxide content for use in a nonferrous-metal smelting furnace |
DE3707884A1 (en) * | 1986-03-13 | 1987-09-17 | Toshiba Ceramics Co | CASTING NOZZLE AND METHOD FOR THEIR PRODUCTION |
FR2595600A1 (en) * | 1986-03-13 | 1987-09-18 | Toshiba Ceramics Co | CASTING NOZZLE AND ITS MANUFACTURE |
US4917276A (en) * | 1987-07-15 | 1990-04-17 | Kurosaki Refractories Co., Ltd. | Sliding gate nozzle for special steel |
EP0323010A2 (en) * | 1987-12-28 | 1989-07-05 | Shinagawa Refractories Co., Ltd. | Carbon containing refractory |
EP0323010A3 (en) * | 1987-12-28 | 1990-05-16 | Shinagawa Refractories Co., Ltd. | Carbon containing refractory |
CN114455941A (en) * | 2022-01-19 | 2022-05-10 | 北京科技大学 | Silicon-corundum-high titanium mullite composite refractory material for blast furnace and preparation method thereof |
CN114455941B (en) * | 2022-01-19 | 2022-12-13 | 北京科技大学 | Silicon-corundum-high titanium mullite composite refractory material for blast furnace and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
DE3048678A1 (en) | 1981-10-01 |
GB2066802B (en) | 1983-05-11 |
US4326040A (en) | 1982-04-20 |
JPS5919067B2 (en) | 1984-05-02 |
JPS5696774A (en) | 1981-08-05 |
DE3048678C2 (en) | 1992-05-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4326040A (en) | Refractory for casting and process for producing same | |
US5403794A (en) | Alumina-zirconia refractory material and articles made therefrom | |
US4585485A (en) | Refractory sliding nozzle plate | |
RU2173308C2 (en) | Method of forming repair refractory compound and powder mix for carrying it trough | |
JPS62297264A (en) | Carbon-bonded refractories | |
US4775504A (en) | Process for producing refractory plate for sliding nozzle | |
AU3784393A (en) | Vibratable refractory composition | |
JP3351998B2 (en) | Sliding nozzle plate and method of manufacturing the same | |
JPH0437466A (en) | Non-calcined plate brick for sliding nozzle | |
JPS6050748B2 (en) | Manufacturing method of highly corrosion resistant continuous casting nozzle | |
JPS5842144B2 (en) | graphite casting nozzle | |
JP3383185B2 (en) | Nozzle for casting | |
CN114514212B (en) | CaO-ZrO 2 Composition, caO-ZrO 2 Method for producing composition, caO-ZrO-containing composition 2 Refractory and casting nozzle | |
JPS608988B2 (en) | Immersion nozzle composition for casting | |
JP2778760B2 (en) | Sliding nozzle plate brick | |
JP2827383B2 (en) | Coating method for kiln interior | |
JPS639908B2 (en) | ||
WO1999047472A1 (en) | Low silica refractory | |
JPH0723254B2 (en) | Refractory material | |
JP2004323265A (en) | Refractory for continuous casting, which inhibits sticking of alumina | |
JPH0541590B2 (en) | ||
JPS6128623B2 (en) | ||
JPS6324945B2 (en) | ||
JPH0285692A (en) | Flame spraying material for industrial kiln | |
JPH028995B2 (en) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19981223 |